Process for the preparation of acyl and alkyl substituted cyclic organic compounds and products resulting therefrom



United States Patent Oflice 3,096,266 Patented July 2, 1963 of New YorkNo Drawing. Filed Mar. 31, 1960, Ser. No. 18,890 Claims priority,application Great Britain Apr. 7, 1959 10 Claims. (Cl. 204-158) Thisinvention relates to the preparation of organic compounds and toproducts resulting therefrom. More particularly, the invention relatesto a process for the preparation of acyl and alkyl substituted cycliccompounds.

The present invention greatly facilitates the synthesis of substitutedor unsubstituted organic compounds in that it provides a new and generalone-step method for this purpose. The invention is predicated upon thediscovery that when certain organo-metallic complexes, as hereinafterdescribed, whose organic part contains a preformed carbon skeleton, arereacted with compounds containing at least one element or reactantcapable of forming stable bonds with the skeleton, the bonding of theelement to the skeleton is readily achieved. The compounds formedthereby are characterized as containing at least one of the carbonskeletons and at least one of the elements.

Although the mechanism of the reaction is not fully understood, basicconsiderations applying to the inventive process can be found in thefollowing discussion. It is believed that organo-rnetallic complexes asfor example, Fe (CO) (RC R) or Fe (CO) (RC R) can be represented by thestructures respectively shown below, wherein the actual meaning of R hasbeen disregarded for the sake of clarity.

as R R l :2: Fe :2 3km co k! C0 )Fe co 8 \0 Cf g Go There are variousevidences which indicate that the two iron atoms contained in theseorgano-rnetallic complexes have different chemical behavior. Inparticular it has been found that the iron atom bonded into the ringsystem can be more readily removed than the other iron atom. It can thusbe foreseen that the splitting of the iron atoms which occurs during thereaction isolates a highly reactive carbon skeleton which can readilyreact with any element capable of forming stable bonding with thatcarbon skeleton. Similar considerations apply to the variousorgano-metallic complexes containing only one metal atom or one (R'C R)group and apply as well to the complexes having a larger number of metalatoms or (R'C R) groups in their structure. It is therefore apparentthat by properly selecting the reactant containing an element capable offorming stable bondings with the carbon skeleton, a large variety oforganic compounds can be provided.

According to this invention, a process for the preparation of acyl oralkyl substituted cyclic compounds comprises reacting an organo-metalliccomplex having the formula: M,,(C0),,(R'C;,R"),,,(B),, with an acylationor alkylation reagent. In the above referred to organo metalliccomplexes, M represents a transition metal belonging to the VI, VII orVIII sub-groups of the periodic table, CO represents a carbonyl group, Rand/or R" may be the same or dilferent and represent hydrogen, orhydroxyl, halogeno, carboalkoxy, alkyl, aryl, cycloaliphatic, alkoxy orsilyl groups and the like, including the substituted derivativesthereof, C represents a carbon-to carbon bonding, B represents a memberselected from the group consisting of hydrogen, mercury, halogen, alkyl,aryl or acyl, x represents an integer of from 1 t0 4, y represents aninteger of from 1 to 10, z represents an integer of from I to 6, and wrepresents an integer of from 0 to 4.

Typical organo-metallic complexes suitable for use in the process ofthis invention include:

Fe (CO) (RC R') wherein R represents a phenyl or ethyl group or ahydrogen atom and wherein R represents a phenyl, methyl, ethyl ormethoxy group or a hydrogen atom.

Fe (CO) (RC R') (B) wherein R and R" represent hydrogen and B representseither hydrogen or a methyl rest. These complexes may be represented bythe following structure:

0C Fe\ is v R Te o o o o o Fe (CO) (RC R)- wherein R and R representphenyl groups. This complex may be represented by the followingstructure:

Fe (CO) (RC R'), wherein R and R represent phenyl groups. This complexmay be represented by the following structure:

Fe(CO) (RC R') wherein R represents a phenyl group and wherein Rrepresents a phenyl group or a hy- 4 drogen atom. This complex may berepresented by the group or a hydrogen atom. This complex may bereprefollowmg structure: sented by the following structure:

R O: R R :R

F0 ss Fe a 3% o o o )a( z w r n R represents a hydrogen Co (CO) (RC R'),wherein R represents a phenyl atom or a phenyl group and wherein Rrepresents a hygroup and R represents a phenyl group or a carbomethoxydrogen atom. This complex may be represented by the group. This complexmay be represented by the followtollowing structure: ing structure:

R R 00 c-0 00 0G C-CR t! \i i/ B OC Co-----Co -CO 2 t R 00 o fi-(pn 00co 0 Co (CO) (RC R') wherein R represents a carboethoxy or methyl groupor a hydrogen atom and wherein R Fe (CO) (RC R) wherein R and Rrepresent phenyl fepfesfllts a p y P Of a trimethylsilyl P- This groups.This complex may be represented by the followwmplex y be repl'fisemed ythe following sin-16mm: ing structure: R

Co (CO) (RC H) Hg, wherein R represents a tertiary butyl ortrimethylsilyl group. This complex may be rep 40 resented by thefollowing structure:

u o i Web--11? -o 1 R La 71 e l l l lit II R

R(H3RO Co (CO) (RC H)4, wherein R represents a tertiary butyl ortrimethylsilyl group. This complex may be represented by the followingstructure:

0 H HO H H H R o R u 0 R C R I! 0 H o o Fe (CO) (RC H) wherein Rrepresents a phenyl group. This complexrnay be represented by thefollowing C03(CO)BH(RC2H) structure:

wherein R represents a phenyl group. This complex may be represented bythe following structure:

c O c Fe(CO) (RC H) wherein R represents a phenyl Ni(CO) (RC R') whereinR and R represent phenyl groups. This complex may be represented by thefollowing structure:

Other useful organo-metallic complexes are those in which the transitionmetal is ruthenium, rhodium, palladium, osmium, iridium, platinum,manganese, rhenium, chromium or tungsten, or are those in which thecarbonyl group bonded to the metal is partially replaced by a nitrosyl,a substituted stibine, a substituted arsine, or a substituted phosphine.

The organo-metallic complexes employed as starting materials in thepresent invention may be conveniently prepared by the process describedin copending application 707,111, entitled, Organo-Metallic Compoundsand Method for Their Preparation, filed January 6, 1958, in the name ofKarl Walter Hubel, the description thereof being incorporated herein byreference.

Briefly stated, the organo-metallic complexes can be prepared byreacting an acetylenic compound with a metal carbonyl in a non-aqueousneutral medium at a temperature of between room and 300 C. As aconsequence, a stable organo-imetallic carbonyl reaction product isformed. The acetylenic reactant has the formula:

wherein R and R" represent a substituent selected from the groupconsisting of hydrogen, an organic group, and substituted derivativesthereof, a functional group and substituted derivatives thereof and anorgano-substituted hydride group, the substituent being substantiallyinert to and inactive with the carbonyl group. The metals of the metalcarbonyl group are selected from the group consisting of iron, nickel,ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese,rhenium, chromium, molybdenum, cobalt and tungsten.

Exemplary of the reagents that may be employed in the process of thisinvention are: acyl halides, anhydrides, alkyl halides, .aryl halides,and olefines with catalysts of the Lewis-type. For the purpose of thisinvention it is preferred to employ benzylchlon'de, alkyl halides,arylalkyl halides and olefines with the aid of catalysts such as borontrifiuoride and the like.

The process of this invention can be carried out using stoichiometricamounts of the starting materials. However, it has been found that anexcess of the aforesaid reactant is generally preferable. The reactionis usually carried out in a polar or non-polar organic solvent such asbenzene, petroleum ether, ether, tetrahydrofuran, betaethoxy ethanol andthe like. When side reactions are to be avoided, the selected solventshould preferably be of an inert kind. However, no addition of solventis necessary when one of the starting materials is liquid at thereaction temperature.

The reaction is usually achieved by heating the reaction mixture, or byactivating the reaction mixture with ultraviolet radiations, or bycombining both heating and ultraviolet radiations. However, whenemploying reactants normally used at relatively low temperatures, it isadvisable to cool the reaction mixture down to 0' C. or lower. Generallyspeaking, the reaction temperature at which the process of thisinvention may be carried out ranges from about -60 C. to about 250 C.The specific temperatures employed will, of course, depend upon thenature of the reactants employed. It is preferable to perform thereaction in a closed system Whenever one of the reactants, or thereaction products formed thereby or the solvent employed, are toovolatile at the reaction temperatures.

The reaction is usually completed within a few hours, although longerreaction times may be necessary in some instances. The reaction productsare easily removable from the reaction mixture after completion of thereaction using any suitable technique. The technique of removal will ofcourse vary according to the nature of the reaction product and theoccurrence of side reactions. Suitable process conditions will befurther illustrated in the specific examples hereinafter describedrelating to the present invention.

Typical compounds prepared by the process of this invention may beillustrated by the following general formula:

CHsR CH R wherein R represents hydrogen or hydroxyl, halogeno,carboalkoxy, alkyl, aryl, cycloaliphatic, alkoxy or silyl groupsincluding the substituted derivatives thereof. These cyclopentaneone orcyclopentenone compounds are by way of illustration only. Many othersimilar cyclic compounds may be produced by the process of thisinvention.

The invention may be further illustrated by the following example:

A solution of 0.96 gram Fe (CO) (C H C C H and 10 ml. benzylchloride in30 ml. dioxane was irradiated in a quartz vessel with ultraviolet lightfor 5 hours at reflux temperature. The filtered reaction mixture wasevaporated to dryness and the residue was chromatographed in benzenesolution. The fraction eluted with a mixture of benzene/ether yielded0.1 grams of colorless crystals having the M.P.=l86-202 C. The analysisand IR. spectrum indicated that two benzyl groups had been added ontetracyclone.

The process of this invention can also be carried out employing asmentioned previously, reactants such as acetyl chloride, ethyl chloride,and the like. As also mentioned previously other solvents besidesbenzene can also be employed in the process of this invention. Exemplaryof such solvents are toluene, normal heptane, or ethylene glycoldimethyl ether. Similarly, other organometallic complexes besides theiron complexes indicated in the example above can also be employed.

The compounds produced by the process of this invention haveart-recognized utility or will serve as intermediates in the productionof compounds having a wide range of art-recognized utility.

For example, the alkyl or acyl substituted cyclic ketonic compounds ofthis invention have utility as polar solvents.

They are also useful as intermediates in the synthesis of fulvenes andas starting material for the production of organo-metallic complexes andin particular, 1r complexes. They are also useful as intermediates forthe production of compounds which have utility as plasticizers orstabilizers.

What is claimed is:

l. A process for the preparation of acyl and alkylsubstituted cyclicorganic compounds free of carbon to metal bonds, which comprisesreacting an organo-metallic complex having the formula:

wherein M is a transition metal selected from the group consisting ofsub-groups VIB, VIIB and VIII of the periodic table, CO represents acarbonyl group, R and R" represent a member selected from the groupconsisting of hydrogen, halogeno, carboalkoxy, alkyl, aryl,cycloaliphatic alkoxy and silyl groups, C represents carbon-to-carbonbonding, B represents a member selected from the group consisting ofhydrogen, mercury, halogen, alkyl, aryl and acyl, 1: represents aninteger of from 1 to 4, y represents an integer of from 1 to 10, zrepresents an integer of from 1 to 6, and w represents an integer offrom O to 4, with at least a stoichiometric amount of a member selectedfrom the group consisting of acylation and alkylation reagents, wherebythe carbon to metal bond in said complex is broken and a member of thegroup consisting of alkyl and aryl is added to the C, group present insaid complex to form the said cyclic organic compound.

2. A process as claimed in claim 1, in which the metal of theorgano-metallic complex is iron.

3. A process as claimed in claim 1, in which the metal of theorgano-metallic complex is cobalt.

4. The process as claimed in claim 1, in which the metal of theorgano-metallic complex is nickel.

5. A process as claimed in claim 1, in which the metal of theorgano-metallic complex is molybdenum.

6. A process as claimed in claim 1, in which the reagent is a memberselected from the group consisting of an acyl halide, an anhydride, analkyl halide, an aryl halide, and an olefine with a catalyst of theLewis-type.

7. A process as claimed in claim 6, in which a stoichiometric excess ofthe reagent is employed.

8. A process as claimed in claim 7, in which an organic solvent selectedfrom the group consisting of benzene, petroleum ether, ether,tetrahydrofuran and beta-ethoxy ethanol is employed.

9. A process as claimed in claim 8, in which the reaction is carried outat a temperature of between C. and 250 C.

10. A process as claimed in claim 1, in which the reaction mixture isinitially activated by ultraviolet radiation.

References Cited in the file of this patent UNITED STATES PATENTS2,849,470 Benson Aug. 26, 1958 2,852,542 Sweeney Sept. 16, 19582,898,359 Leedham et al Aug. 4, 1959 2,916,503 Kozikowski Dec. 8, 1959

1. A PROCESS FOR THE PREPARATION OF ACYL AND ALKYLSUBSTITUTED CYCLICORGANIC COMPOUNDS FREE OF CARBON TO METAL BONDS, WHICH COMPRISESREACTING AN ORGANO-METALLIC COMPLEX HAVING THE FORMULA:
 10. A PROCESS ASCLAIMED IN CLAIM 1, IN WHICH THE REACTION MIXTURE INITIALLY ACTIVATED BYULTRAVIOLET RADIATION.